全文获取类型
收费全文 | 731篇 |
免费 | 67篇 |
国内免费 | 94篇 |
专业分类
化学 | 729篇 |
晶体学 | 23篇 |
力学 | 8篇 |
综合类 | 4篇 |
数学 | 19篇 |
物理学 | 109篇 |
出版年
2025年 | 2篇 |
2024年 | 13篇 |
2023年 | 12篇 |
2022年 | 32篇 |
2021年 | 59篇 |
2020年 | 71篇 |
2019年 | 70篇 |
2018年 | 33篇 |
2017年 | 22篇 |
2016年 | 32篇 |
2015年 | 23篇 |
2014年 | 25篇 |
2013年 | 35篇 |
2012年 | 34篇 |
2011年 | 33篇 |
2010年 | 31篇 |
2009年 | 24篇 |
2008年 | 26篇 |
2007年 | 28篇 |
2006年 | 32篇 |
2005年 | 16篇 |
2004年 | 26篇 |
2003年 | 25篇 |
2002年 | 19篇 |
2001年 | 23篇 |
2000年 | 15篇 |
1999年 | 16篇 |
1998年 | 16篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 7篇 |
1993年 | 8篇 |
1992年 | 10篇 |
1991年 | 12篇 |
1990年 | 4篇 |
1989年 | 8篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1974年 | 2篇 |
排序方式: 共有892条查询结果,搜索用时 0 毫秒
41.
42.
Adsorption of hydrogen ions from aqueous NaCl solutions at the Pyrex glass-water interface was investigated by acid-base titration (glass electrode) at 25 degrees C and at the ionic strengths 0.010, 0.030, 0.10, 1.0, and 3.0 mol dm(-3). The pH values ranged from 2 to 7. The Pyrex samples had a specific surface area of 19.2x10(3) m(2)kg(-1) and a porous structure (pores 2.4 nm thick, 280 nm long). The reactions were found to be extremely slow but showed good reversibility. The potentiometric data, due to the small effect of ionic strength on the equilibria, were fitted with a simple nonelectrostatic model based on strong specific interactions of medium ions with deprotonated silanol, >SiO(-), and boranol, >BO(-), as well as with protonated sites. The acid-base properties are described by the reactions and equilibrium constants at the infinite dilution reference state: >SiONa + H(+) <==> >SiOHNa(+), logbeta110Si=3.1+/-0.2; >SiONa + 2H(+) + Cl(-) <==> >SiOH(2)Cl + Na(+), logbeta201Si=6.75+/-0.15; >SiONa + H(+) <==> >SiOH + Na(+), logbeta100Si=1.8+/-0.2, >BONa + H(+) <==>BOH + Na(+), logbeta100B=6.4+/-0.2; >BONa + H(+) <==> >BOHNa(+), logbeta110B=6.6+/-0.2; >BONa + 2H(+) <==> >BOH(+)(2) + Na(+), logbeta200B=11.56+/-0.15. 相似文献
43.
A Mössbauer study of systems Co x Mn3?x?y Fe y O4 and Ni x Mn3?x?y Fe y O4 for values ofx=0·1, 0·5, 1·0 andy ranging from 0·1 to 2·0 in steps of 0·2 have been made. At room temperature samples fory values ranging in between 0·1 to 0·5 exhibit paramagnetic behaviour while all spectra for values ofy between 0·6 to 0·8 show relaxation effects. Well-defined hyperfine Zeeman spectra are observed for all the samples withy>0·8 and resolved in two sextets corresponding to octahedral and tetrahedral site symmetries and a central doublet probably due to the presence of super-paramagnetic particles in the system. The hyperfine field at57Fe nucleus reduces with decreasing iron cobalt and nickel concentration. These observations have been explained in terms of site preference of cations and exchange interactions. 相似文献
44.
Anne Tscheliessnig Danny Ong Jeremy Lee Siqi Pan Gernalia Satianegara Kornelia Schriebl Andre Choo Alois Jungbauer 《Journal of chromatography. A》2009,1216(45):7851-7864
A two-step purification strategy comprising of polyethylene glycol (PEG) precipitation and anion-exchange chromatography was developed for a panel of monoclonal immunoglobulin M (IgM) (pI 5.5–7.7) produced from hybridoma cultures. PEG precipitation was optimized with regards to concentration, pH and mixing. For anion-exchange chromatography, different resins were screened of which Fractogel EMD, a polymer grafted porous resin had the highest capacity. Despite its significantly slower mass transfer, the binding capacity was still higher compared to a convection driven resin (monolith). This purification strategy was successfully demonstrated for all 9 IgMs in the panel. In small scale most antibodies could be purified to >95% purity with the exception of two which gave a lower final purity (46% and 85%). The yield was dependent on the different antibodies ranging from 28% to 84%. Further improvement of recovery and purity was obtained by the digestion of DNA present in the hybridoma supernatant using an endonuclease, benzonase. So far this strategy has been applied for the purification of up to 2 l hybridoma supernatants. 相似文献
45.
Single atom catalysts (SACs) have attracted much attention in recent years. As an essential group in SACs, M−X−C (X=nonmetallic element) materials have been demonstrated to be efficient in many reactions. However, identifying the active sites on M−X−C, especially under working conditions, is still challenging, which is crucial for chemists to further understand the mechanism underlying the reaction and better design proper SACs for specific reactions. Herein, the types and characterization of M−X−C are comprehensively summarized and discussed in this review. In addition to the basic information above, the challenges and opportunities remaining in this field will be also proposed to present a perspective to the research on the next step. 相似文献
46.
Dr. Chongqi Chen Hongju Ren Yuanyuan He Dr. Yingying Zhan Prof. Chaktong Au Dr. Yu Luo Prof. Xingyi Lin Dr. Shijing Liang Prof. Lilong Jiang 《ChemCatChem》2020,12(18):4672-4679
CuOx/SiO2 precursor was successfully fabricated by an ammonia evaporation hydrothermal method. Upon reduction in 5 vol % H2/N2 at 250, 300, 350, 400, or 450 °C, CuO and copper phyllosilicate species in the precursor bring about the formation of highly dispersed Cu0 and Cu+ species, respectively. The Cu+/Cu0 ratios were studied by XAES technique, while the particle sizes were estimated on the basis of HRTEM images. It is disclosed that the ratios and particle sizes varied with CuOx/SiO2 reduction temperatures. The results of in situ DRIFTS and XAES characterization reveal that both Cu0 and Cu+ are active for CO adsorption and water dissociation, especially so with Cu0 and Cu+ particles of small sizes. It was also observed that the adsorption of CO on Cu+ is stronger than that on Cu0, and Cu0 is more active than Cu+ for water dissociation. Among the prepared Cu/SiO2 catalysts, the one resulted from precursor reduction at 300 °C shows the highest CO conversion in WGS reaction, which is attributed to the small size of Cu0 (2.45 nm) and the large amount of Cu+. 相似文献
47.
Xiaoya Wang Bingbing Liu Jie Li Yunyun Zhai Haiqing Liu Lei Li Herui Wen 《Electroanalysis》2021,33(6):1484-1490
2D metal-organic framework (MOF) has potential applications in electrocatalysis owing to fast mass transfer, charge transfer and large specific surface area. Here, we had prepared three conductive 2D MOF based on Ni, NiCo and Co in a simple and rapid way. The 2D nanostructure of MOF was confirmed by SEM and TEM. The chemical composition was studied by XRD, Raman and XPS spectrum. The electrochemical oxidation and detection was investigated through cyclic voltammetry and current-time method. Their sensing performance for urea was determined by varying oxidation potentials and metal sites. The non-enzymatic Ni-, NiCo- and Co-MOF sensors had good catalytic activity for urea. Compared with NiCo- and Co-MOF, Ni-MOF had a wider linear range (0.5–832.5 μM), high sensitivity (1960 μA mM−1 cm−2), low detection limit (0.471 μM), and fast response time. The sensors had well repeatability, reproducibility, and selectivity to specific interfering species. Furthermore, Ni- and NiCo-MOF modified electrode was also applied to detection of milk samples. The results showed that the recovery was satisfactory, which further confirmed the effectiveness of non-enzyme sensor. In general, the highly-sensitive 2D Ni- and NiCo-MOF modified electrode has great potential as nonenzymatic urea sensors for real samples detection in hydrogen energy, clinical diagnostics, and environmental protection, et al. 相似文献
48.
Formylation is one of the newly discovered post-translational modifications in lysine residue which is responsible for different kinds of diseases. In this work, a novel predictor, named predForm-Site, has been developed to predict formylation sites with higher accuracy. We have integrated multiple sequence features for developing a more informative representation of formylation sites. Moreover, decision function of the underlying classifier have been optimized on skewed formylation dataset during prediction model training for prediction quality improvement. On the dataset used by LFPred and Formator predictor, predForm-Site achieved 99.5% sensitivity, 99.8% specificity and 99.8% overall accuracy with AUC of 0.999 in the jackknife test. In the independent test, it has also achieved more than 97% sensitivity and 99% specificity. Similarly, in benchmarking with recent method CKSAAP_FormSite, the proposed predictor significantly outperformed in all the measures, particularly sensitivity by around 20%, specificity by nearly 30% and overall accuracy by more than 22%. These experimental results show that the proposed predForm-Site can be used as a complementary tool for the fast exploration of formylation sites. For convenience of the scientific community, predForm-Site has been deployed as an online tool, accessible at http://103.99.176.239:8080/predForm-Site. 相似文献
49.
Zhichao Hao Dr. Zhengang Guo Dr. Mengnan Ruan Prof. Jing Ya Yong Yang Dr. Xiangfeng Wu Prof. Zhifeng Liu 《ChemCatChem》2021,13(1):271-280
The enhanced separation and injection efficiencies of photogenerated carriers is essential to improve the photoelectrochemical (PEC) performance of WO3 photoanode. In this work, we firstly synthesized WO3/NiCo2O4 heterojunction through simple hydrothermal-annealing method as well as investigate the effect and mechanism of NiCo2O4 on WO3 for PEC performances. The measurements demonstrate that the nano-needle NiCo2O4 grown on the surface of WO3 induces the bimetallic Ni/Co redox reaction sites extensively exposed to the electrolyte, which is beneficial to enhance the PEC performances of WO3 photoanode, such as photocurrent density improved by four times (0.84 mA/cm2 at 1.23 V vs. RHE) as well as more negative initial potential (∼280 mV) in contrast to bare WO3. Further investigation shows the remarkable enhancement of PEC performances is attributed to improved surface reaction kinetics, the enhanced injection efficiency and separation efficiency of photogenerated carriers due to the co-catalyst effect of NiCo2O4 and the formation of WO3/NiCo2O4 heterojunction. This work provides reference for application of heterojunction with co-catalyst function, which is beneficial to the development and application of similar structures. 相似文献
50.
Chenglin Miao Fengyu Zhang Luoyu Cai Tianli Hui Junting Feng Dianqing Li 《ChemCatChem》2021,13(23):4937-4947
Focusing on the simultaneous enhancement of activity and selectivity in α, β-unsaturated aldehyde hydrogenation, we designed and prepared an ultrathin CoAl-LDH supported Pt catalyst. A series of technologies revealed the ultrathin CoAl-LDH support possesses the characteristic of dual defects, oxygen vacancy (VO) and cobalt vacancy (VCo). Then, two kinds of vacancy related interface sites were identified, namely Pt−VO−Coδ+ and Pt−VCo−OHδ−. Compared with the bulk catalyst, the ultrathin catalyst exhibits both enhanced intrinsic activity and C=O bond selectivity under the synergistic effect of the dual interface sites. Specifically, the Pt−VO−Coδ+ interface site changes the adsorption mode of cinnamaldehyde and promotes the activation of C=O bonds, thus leading to the improved cinnamyl alcohol selectivity. The H atoms of the Pt−VCo−OHδ− interface site participate in the hydrogenation process, which facilitates the mobility of active hydrogen and therefore promotes the intrinsic activity. More importantly, the ultrathin catalyst shows good reusability. 相似文献